CN109659618A - A kind of electrolysis additive, electrolyte and preparation method thereof, lithium ion battery and equipment - Google Patents
A kind of electrolysis additive, electrolyte and preparation method thereof, lithium ion battery and equipment Download PDFInfo
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- CN109659618A CN109659618A CN201811636106.5A CN201811636106A CN109659618A CN 109659618 A CN109659618 A CN 109659618A CN 201811636106 A CN201811636106 A CN 201811636106A CN 109659618 A CN109659618 A CN 109659618A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of electrolysis additive, electrolyte and preparation method thereof, lithium ion battery and equipment.Electrolysis additive of the present invention includes compound shown in formula (I):In formula (I), R1, R2, R3, R4It is independently selected from the alkyl of C1~C50, the naphthenic base of C3~C50, the alkenyl of C2~C50, any one of alkynyl or the aryl of C6~C50 of C2~C50；Wherein, R1, R2, R3, R4Upper arbitrary hydrogen atom is optional substituted or non-substituted；Alternatively, in formula (I), R1And R2And R3And R4Independently optional key and, and ring is collectively formed with neighbouring oxygen atom；Wherein, arbitrary hydrogen atom is optional substituted or non-substituted on the ring.In the present invention, using pyrosulfuric acid ester and pyrosulfuric acid ester type compound as electrolysis additive, the service performance of lithium ion battery under the high temperature conditions can be effectively improved and improved.
Description
Technical field
The present invention relates to field of lithium ion battery, in particular to a kind of electrolysis additive, electrolyte and its preparation
Method, lithium ion battery and equipment.
Background technique
In order to cope with the energy crisis and environmental problem that get worse, lithium ion battery is as important cleaning in recent years
Chemical energy source gradually starts large-scale application in fields such as electric car, energy-accumulating power stations.The service life and safety problem of battery
It is the core technology of power battery, while considers territorial environment difference, it is also what power battery needed to capture that high/low temperature, which is taken into account,
Technical problem.
In non-aqueous electrolyte lithium ion battery, nonaqueous electrolytic solution is the key factor for influencing battery high temperature performance, special
Not, the additive in nonaqueous electrolytic solution is even more important to the performance of battery high temperature performance.Current commercialized non-aqueous solution electrolysis
In liquid, such as traditional film for additive of vinylene carbonate (VC) is added, mainly to guarantee the cycle performance of battery.But
The high voltage stability of VC is poor, under high voltage condition, is difficult to meet the performance requirement of 45 DEG C of circulations.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of electrolysis additive, to solve existing electrolysis additive in high temperature
Existing deficiency on cycle performance.
The second object of the present invention is to provide the lithium-ion electrolyte for containing electrolysis additive of the present invention described in one kind.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of electrolysis additive, the electrolysis additive include the compound as shown in following formula (I):
In formula (I) compound, R1, R2, R3, R4It is independently selected from the alkyl of C1~C50, the naphthenic base of C3~C50,
The alkenyl of C2~C50, any one of alkynyl or the aryl of C6~C50 of C2~C50；Wherein, R1, R2, R3, R4It is upper any
Hydrogen atom it is optional be substituted or it is non-substituted；
Alternatively, in formula (I), R1And R2And R3And R4Independently optional key and, and it is common with neighbouring oxygen atom
Form ring；Wherein, arbitrary hydrogen atom is optional substituted or non-substituted on the ring.
Preferably, in electrolysis additive of the present invention, in formula (I) compound, R1, R2, R3, R4Independently
The alkyl selected from C1~C30, the naphthenic base of C3~C30, C2~C30 alkenyl, the alkynyl of C2~C30 or C6~C30's
Any one of aryl；Preferably, in formula (I) compound, R1, R2, R3, R4It is independently selected from alkyl, the C3 of C1~C12
The alkenyl of the naphthenic base of~C12, C2~C12, any one of alkynyl or the aryl of C6~C20 of C2~C12.
Preferably, in electrolysis additive of the present invention, shown in formula (I) compound structure such as following formula (II)；
In formula (II), R5, R6, R7, R8, R9, R10, R11, R12It is independently selected from hydrogen, the alkyl of C1~C50, C3~C50
Naphthenic base, the alkenyl of C2~C50, any one of alkynyl or the aryl of C6~C50 of C2~C50；Wherein, work as R5, R6,
R7, R8, R9, R10, R11, R12In at least one R base when not being hydrogen, this is not the optional quilt of arbitrary hydrogen atom on the R base of hydrogen
Replace or non-substituted.
Preferably, in electrolysis additive of the present invention, in formula (II), R5, R6, R7, R8, R9, R10, R11, R12Point
Not it is independent be selected from hydrogen, the alkyl of C1~C30, the naphthenic base of C3~C30, the alkenyl of C2~C30, the alkynyl of C2~C30, or
Any one of aryl of C6~C30；Preferably, in formula (II) compound, R5, R6, R7, R8, R9, R10, R11, R12Independently
Be selected from hydrogen, the alkyl of C1~C12, the naphthenic base of C3~C12, the alkenyl of C2~C12, the alkynyl or C6 of C2~C12~
Any one of aryl of C20；Wherein, work as R5, R6, R7, R8, R9, R10, R11, R12In at least one R base when not being hydrogen, this is not
Arbitrary hydrogen atom is optional substituted or non-substituted on the R base of hydrogen.
Preferably, in electrolysis additive of the present invention, shown in formula (II) compound structure such as following formula (III):
In formula (III), R6, R7, R10, R11It is independently selected from the alkyl of C1~C12, the naphthenic base of C3~C12, C2~
The alkenyl of C12, any one of alkynyl or the aryl of C6~C20 of C2~C12；Wherein, R6, R7, R10, R11It is upper arbitrary
Hydrogen atom is optional substituted or non-substituted.
A kind of electrolyte, the electrolyte include electrolysis additive of the present invention and basic electrolyte.
Preferably, in electrolyte of the present invention, the quality of electrolysis additive be basic electrolyte quality 0.01~
5%；It wherein, include carbonate solvent and lithium salts in the basic electrolyte；Preferably, the quality of electrolysis additive is base
The 0.05~3% of plinth electrolyte quality.
A method of preparing electrolyte of the present invention, comprising: electrolysis additive of the present invention is added into basic electrolyte,
Obtain electrolyte.
Meanwhile present invention provides the lithium ion batteries comprising electrolyte of the present invention.
Further, the present invention also provides the equipment driven by lithium ion battery of the present invention.
Compared with prior art, the invention has the benefit that
In the present invention, using pyrosulfuric acid ester and pyrosulfuric acid ester type compound as electrolysis additive, can be effectively improved and
Improve the service performance of lithium ion battery under the high temperature conditions.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Electrolysis additive provided by the present invention is that a kind of pyrosulfuric acid ester and pyrosulfuric acid ester type compound electrolyte add
Add agent, in the prior art there is no using such compound as electrolysis additive, is electrolysed with improving nonaqueous lithium ion battery
The related of the high temperature cyclic performance of liquid is attempted.
Electrolysis additive provided by the present invention, structure are as follows:
In certain embodiments of the present invention, in the electrolysis additive compound as shown in above formula (I) structure, R1,
R2, R3And R4Between independently of one another.
In this embodiment, in formula (I), R1, R2, R3, R4It is independently selected from the alkyl of C1~C50, C3~C50
Naphthenic base, the alkenyl of C2~C50, any one of alkynyl or the aryl of C6~C50 of C2~C50；
Wherein, R as above1, R2, R3, R4Upper arbitrary hydrogen atom is optional by the alkyl of C1~C50, the ring of C3~C50
The alkenyl of alkyl, C2~C50, the alkynyl of C2~C50 or the aryl of C6~C50 are substituted or non-substituted；
Preferably, in formula (I), R1, R2, R3, R4It is independently selected from the alkyl of C1~C30, the naphthenic base of C3~C30,
The alkenyl of C2~C30, any one of alkynyl or the aryl of C6~C30 of C2~C30；
Wherein, R as above1, R2, R3, R4Upper arbitrary hydrogen atom is optional by the alkyl of C1~C30, the ring of C3~C30
The alkenyl of alkyl, C2~C30, the alkynyl of C2~C30 or the aryl of C6~C30 are substituted or non-substituted；
It is furthermore preferred that in formula (I), R1, R2, R3, R4It is independently selected from the alkyl of C1~C12, the cycloalkanes of C3~C12
Base, the alkenyl of C2~C12, any one of alkynyl or the aryl of C6~C20 of C2~C12；
Wherein, R as above1, R2, R3, R4Upper arbitrary hydrogen atom is optional by the alkyl of C1~C12, the ring of C3~C12
The alkenyl of alkyl, C2~C12, the alkynyl of C2~C12 or the aryl of C6~C20 are substituted or non-substituted；
Particularly, in formula (I), R1, R2, R3, R4It is independently selected from alkyl (such as the methyl, ethyl, just of C1~C5
Propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl etc.), the cycloalkanes of C3~C5
Base (for example, cyclopropyl, cyclobutyl, cyclopenta etc.), the alkenyl of C2~C5 is (for example, vinyl, allyl, isopropenyl, amylene
Base etc.), the alkenyl (for example, acetenyl, propargyl, isopropynyl, pentynyl etc.) of C2~C5 or the aryl (example of C6~C10
Any one of such as phenyl, tolyl, ethylbenzene, benzyl, naphthalene)；
Wherein, R1, R2, R3, R4Upper arbitrary hydrogen atom is optional by the alkyl of C1~C5, the naphthenic base of C3~C5, C2
Replaced the alkenyl of~C5, the alkynyl of C2~C5 or the aryl of C6~C10.
In other embodiments of the invention, in electrolysis additive compound shown in formula (I) structure, R1And R2,
And R3And R4Independently optional key and, and five yuan or hexa-atomic of ring is collectively formed with neighbouring oxygen atom；
Wherein, arbitrary hydrogen atom is optional substituted or non-substituted on the ring.
Preferably, in this embodiment, shown in formula (I) compound structure such as following formula (II):
In the formula (II) of structure as above, R5, R6, R7, R8, R9, R10, R11, R12It is independently selected from hydrogen, the alkane of C1~C50
Base, the naphthenic base of C3~C50, the alkenyl of C2~C50, any one of alkynyl or the aryl of C6~C50 of C2~C50；
Wherein, work as R5, R6, R7, R8, R9, R10, R11, R12In at least one R base when not being hydrogen, this is not that the R base of hydrogen is taken up an official post
The optional alkyl by C1~C50 of the hydrogen atom of meaning, the naphthenic base of C3~C50, the alkenyl of C2~C50, the alkynes of C2~C50
The aryl of base or C6~C50；
Preferably, in formula (II), R5, R6, R7, R8, R9, R10, R11, R12It is independently selected from hydrogen, the alkyl of C1~C30,
The naphthenic base of C3~C30, the alkenyl of C2~C30, any one of alkynyl or the aryl of C6~C30 of C2~C30；
Wherein, work as R5, R6, R7, R8, R9, R10, R11, R12In at least one R base when not being hydrogen, this is not that the R base of hydrogen is taken up an official post
The hydrogen atom of meaning it is optional by the alkyl of C1~C30, the naphthenic base of C3~C30, C2~C30 alkenyl, the alkynes of C2~C30
The aryl of base or C6~C30 are substituted or non-substituted；
It is furthermore preferred that in formula (II), R5, R6, R7, R8, R9, R10, R11, R12It is independently selected from hydrogen, the alkane of C1~C12
Base, the naphthenic base of C3~C12, the alkenyl of C2~C12, any one of alkynyl or the aryl of C6~C20 of C2~C12；
Wherein, work as R5, R6, R7, R8, R9, R10, R11, R12In at least one R base when not being hydrogen, this is not that the R base of hydrogen is taken up an official post
The hydrogen atom of meaning it is optional by the alkyl of C1~C12, the naphthenic base of C3~C12, C2~C12 alkenyl, the alkynes of C2~C12
The aryl of base or C6~C20 are substituted or non-substituted；
Particularly, in formula (II), R5, R6, R7, R8, R9, R10, R11, R12It is independently selected from hydrogen, the alkyl of C1~C5
(such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl
Deng), the naphthenic base (for example, cyclopropyl, cyclobutyl, cyclopenta etc.) of C3~C5, the alkenyl of C2~C5 is (for example, vinyl, allyl
Base, isopropenyl, pentenyl etc.), the alkenyl (for example, acetenyl, propargyl, isopropynyl, pentynyl etc.) of C2~C5, or
Any one of aryl (such as phenyl, tolyl, ethylbenzene, benzyl, naphthalene etc.) of C6~C10；
Wherein, work as R5, R6, R7, R8, R9, R10, R11, R12In at least one R base when not being hydrogen, this is not that the R base of hydrogen is taken up an official post
The hydrogen atom of meaning it is optional by the alkyl of C1~C5, the naphthenic base of C3~C5, C2~C5 alkenyl, the alkynyl of C2~C5, or
Replaced the aryl of person C6~C10.
In currently preferred some embodiments, in formula (II) compound, R5, R8, R9, R12It is hydrogen, that is, at this
In embodiment, the present invention provides a kind of electrolysis additives such as following formula (III) structure:
In formula (III), R6, R7, R10, R11It is independently selected from the alkyl of C1~C12, the naphthenic base of C3~C12, C2~
The alkenyl of C12, any one of alkynyl or the aryl of C6~C20 of C2~C12；
Wherein, R6, R7, R10, R11The upper optional alkyl by C1~C12 of arbitrary hydrogen atom, the cycloalkanes of C3~C12
Base, the alkenyl of C2~C12, alkynyl or C6~C20 substitution or non-substituted of C2~C12；
Particularly, in formula (III) compound, R6, R7, R10, R11It is independently selected from alkyl (such as the first of C1~C5
Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl etc.), C3
The naphthenic base (for example, cyclopropyl, cyclobutyl, cyclopenta etc.) of~C5, the alkenyl of C2~C5 is (for example, vinyl, allyl, different
Acrylic, pentenyl etc.), the alkenyl (for example, acetenyl, propargyl, isopropynyl, pentynyl etc.) or C6 of C2~C5~
Any one of aryl (such as phenyl, tolyl, ethylbenzene, benzyl, naphthalene etc.) of C10；
Wherein, R6, R7, R10, R11Upper arbitrary hydrogen atom it is optional by the alkyl of C1~C5, C3~C5 naphthenic base,
Replaced the alkenyl of C2~C5, the alkynyl of C2~C5 or the aryl of C6~C10.
In the electrolysis additive compound of present invention arbitrary structures as above, contained [P] structure can be lived by capture
Property generates (anode film forming) CEI film containing P-O key to terminate the chain reaction of organic matter thermal decomposition, and this film
It is more stable, it can play the role of improving cycle performance of lithium ion battery；Meanwhile CEI film can also capture anode dissolution
Ni, thus lithium ion battery of the electrolysis additive of the present invention especially suitable for nickelic system.
Based on the electrolysis additive of as above arbitrary structures of the invention, the present invention also provides add added with the electrolyte
The electrolyte of agent.The electrolyte contains basic electrolyte and is equivalent to basic electrolyte quality 0.01~5% (preferably 0.05
~3%) electrolysis additive of the present invention is constituted；
It wherein, include cyclic carbonate solvents, linear carbonates solvent and lithium salts in the basic electrolyte.
In certain embodiments of the present invention, the cyclic carbonate solvents are ethylene carbonate (EC) and propylene carbonate
At least one of ester (PC)；
Preferably, the linear carbonate solvent includes dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) carbonic acid two
At least one of methyl esters (DEC) and methyl propyl carbonate (MPC)；
Preferably, the mass ratio of the cyclic carbonate solvents and linear carbonate solvent is 1::4~2:3.
In certain embodiments of the present invention, the lithium salts is selected from lithium hexafluoro phosphate (LiPF6), difluorophosphate
(LiPF2O2), LiBF4 (LiBF4), dioxalic acid lithium borate (LiDFOB), trifluoromethyl sulfonic acid lithium (LiSO3CF3), double three
Methyl fluoride sulfimide lithium (Li (CF3SO2)2N)。
In certain embodiments of the present invention, it in electrolyte (being added with electrolysis additive of the present invention) of the present invention, leads
The concentration of electric lithium salts is 1.0mol/L.
Further, the preparation method of above-mentioned electrolyte is additionally provided in the present invention, included the following steps:
(1) after cyclic carbonate solvents and linear carbonate solvent being mixed into mixed solvent respectively, clarification is removed
Water；
(2) at room temperature, electric conducting lithium salt is added in step (1) obtained solvent, obtains basic electrolyte；
(3) it is added in (2) general electrolytic liquid that step obtains and is equivalent to basic electrolyte quality 0.01~5.0% (preferably
Be 0.05~3%) additive, obtain electrolyte of the present invention.
In certain embodiments of the present invention, in preparation method as provided above, step (1) described in purifying remove
Miscellaneous, water removal refers to through molecular sieve, active carbon, calcium hydride, lithium hydride, anhydrous calcium oxide, calcium chloride, phosphorus pentoxide, alkali gold
At least one of category or alkaline-earth metal are handled；
Wherein, the molecular sieve can useType,Type orType is preferably selectedType orType.
Further, the present invention also provides the electrolyte added with electrolysis additive of the present invention in the lithium secondary battery
Application, and include the electrolyte lithium secondary battery have good charge-discharge performance and high and low temperature cycle performance.
It then include: the electrolyte of the present invention as obtained by method as above, containing anode in lithium secondary battery as described above
The positive plate of active material, the negative electrode tab containing negative electrode active material and diaphragm.
In certain embodiments of the present invention, the positive plate further includes binder and conductive agent, will include anode
The anode sizing agent of active material, binder and conductive agent is coated on plus plate current-collecting body, obtains anode after anode sizing agent is dry
Piece.
In certain embodiments of the present invention, the negative electrode tab further includes binder and conductive agent, will include cathode
The negative electrode slurry of active material, binder and conductive agent is coated on negative current collector, obtains cathode after negative electrode slurry is dry
Piece.
In certain embodiments of the present invention, the positive electrode active materials can be with are as follows: cobalt acid lithium LiCoO2, nickel cobalt mangaic acid
Lithium ternary material, LiFePO 4, LiFePO4 (LiFePO4), LiMn2O4 (LiMnO2One of), it can also will wherein extremely
Few two kinds of materials mixing is used as positive electrode active materials, such as LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.2Mn0.3O2Or
LiNi0.6Co0.2Mn0.2O2Deng.
In certain embodiments of the present invention, the negative electrode active material is graphite and/or silicon materials.
In certain embodiments of the present invention, the specific type of the diaphragm is not exposed to specific limitation, can be
Any diaphragm material used in existing lithium ion battery, such as polyethylene, polypropylene, Kynoar and their multilayer
Composite membrane.
Lithium secondary battery of the present invention with structure as described above can be further used in corresponding lithium electrically-actuated device,
Such as: the portable electronic instruments equipment such as mobile phone, video camera, laptop；Or electric car, Wireless Power Tools etc. are big
Type equipment.
Embodiment 1
(1) preparation of electrolyte
(the H in the glove box of argon atmosphere2O < 1ppm, O2< 1ppm), by cyclic carbonate solvents carbonic acid ethynyl ester
(EC) and linear carbonate solvent methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) EC:EMC:DEC=in mass ratio
3:5:2 mixing, with LiPF6Two thiopyrophosphate of neopentyl glycol (DDPS) of gross mass 0.3%, stirring is added in (1M) mixing
Uniformly, lithium-ion electrolyte of the present invention is obtained.
(2) preparation of anode pole piece
By Li [Ni0.6Mn0.2Co0.2]O2: PVDF:SP=94.5:1.5:4 is uniformly mixed with 1-Methyl-2-Pyrrolidone,
After the slurry being blended is coated on the two sides of aluminium foil, anode pole piece is obtained after drying, roll-in；
(3) preparation of cathode pole piece
By graphite: SP:CMC:SBR=95.3:1.5:1.4:1.8 is dissolved in aqueous solution, is uniformly mixed, with the slurry that will be blended
After material is coated on the two sides of copper foil, cathode pole piece is obtained after drying, roll-in.
(4) preparation of lithium ion battery
Square electric is made with winding method in anode pole piece, cathode pole piece and diaphragm prepared by above-mentioned steps (1)-(3)
The electrolyte of above-mentioned preparation is perfused using polymer packaging in core, and it is 1600mAh's that capacity is made after the processes such as chemical conversion, partial volume
Lithium ion battery.
Embodiment 2, comparative example 1
In addition to the following table 1 parameter, other parameters of embodiment 2 and comparative example 1 and the preparation method is the same as that of Example 1.
1 embodiment 2 of table, 1 electrolyte composition parameter of comparative example
| Main solvent | Additive | Lithium salts | |
| Embodiment 2 | EC:EMC:DEC=3:6:1 | 0.3% 2 thiopyrophosphate tetra-ethyl ester | 1.0mol/L |
| Comparative example 1 | EC:EMC:DEC=3:5:2 | 1.5% carbonic acid Asia ethynyl ester (VC) | 1.0mol/L |
Cycle performance test: charge and discharge cycles test, cut-off are carried out to battery with the multiplying power of 1C/1C charge and discharge at 45 DEG C
3.0~4.35V of voltage range.
(i) high-temperature storage is tested: the battery for first finishing chemical conversion is primary with 1C charge and discharge under normal temperature state, then with 1C
By the fully charged rear test internal resistance of battery, high temperature storage is carried out under the conditions of 60 DEG C；
After battery is completely cooling, by the battery testing internal resistance of taking-up, discharge test is carried out with 1C；
(ii) low temperature discharge is tested: the battery for first finishing chemical conversion is primary with 1C charge and discharge under normal temperature state, then with
1C by battery it is fully charged after again under the conditions of -20 DEG C/0.5C under discharge.
Test result is as follows shown in table:
By test data in upper table it is found that lithium ion battery is after high-temperature storage after using electrolyte of the present invention addition
Capacity retention ratio and low temperature electricity rate (compare discharge rate ratio under room temperature after internal resistance increase rate, Capacitance Shift Rate, and circulation
Value) etc. be superior to comparative example in performance parameters.The use of electrolyte addition of the present invention significantly improves lithium ion battery in high temperature
With the service performance under cryogenic conditions.
It can also obviously be learnt by check experiment result as above, the use of electrolysis additive of the present invention will not draw
The raising of lithium ion battery internal resistance is played, and the cycle performance and charge of lithium ion battery are kept for lower internal resistance and capacity
For the raisings of performance parameters such as recovery, all it is advantageous.Thus, the use of electrolysis additive through the invention, Neng Gouyou
Effect improves service performance of the lithium ion battery under low temperature and hot conditions.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of electrolysis additive, which is characterized in that the electrolysis additive includes the compound as shown in following formula (I):
In formula (I), R1, R2, R3, R4It is independently selected from the alkyl of C1~C50, the naphthenic base of C3~C50, the alkene of C2~C50
Base, any one of alkynyl or the aryl of C6~C50 of C2~C50；
Wherein, R1, R2, R3, R4Upper arbitrary hydrogen atom is optional substituted or non-substituted；
Alternatively, in formula (I), R1And R2And R3And R4Independently optional key and, and be collectively formed with neighbouring oxygen atom
Ring；
Wherein, arbitrary hydrogen atom is optional substituted or non-substituted on the ring.
2. electrolysis additive according to claim 1, which is characterized in that in formula (I), R1, R2, R3, R4Independently
The alkenyl of the naphthenic base of alkyl, C3~C30 selected from C1~C30, C2~C30, the alkynyl of C2~C30 or the virtue of C6~C30
Any one of base；
Preferably, in formula (I), R1, R2, R3, R4Be independently selected from the alkyl of C1~C12, the naphthenic base of C3~C12, C2~
The alkenyl of C12, any one of alkynyl or the aryl of C6~C20 of C2~C12.
3. electrolysis additive according to claim 1, which is characterized in that formula (I) the compound structure such as following formula
(II) shown in；
In formula (II), R5, R6, R7, R8, R9, R10, R11, R12It is independently selected from hydrogen, the alkyl of C1~C50, the ring of C3~C50
Alkyl, the alkenyl of C2~C50, any one of alkynyl or the aryl of C6~C50 of C2~C50；
Wherein, work as R5, R6, R7, R8, R9, R10, R11, R12In at least one R base when not being hydrogen, this is not arbitrary on the R base of hydrogen
Hydrogen atom is optional substituted or non-substituted.
4. electrolysis additive according to claim 3, which is characterized in that in formula (II), R5, R6, R7, R8, R9, R10,
R11, R12It is independently selected from hydrogen, the alkyl of C1~C30, the naphthenic base of C3~C30, the alkenyl of C2~C30, C2~C30's
Any one of alkynyl or the aryl of C6~C30；
Preferably, in formula (II), R5, R6, R7, R8, R9, R10, R11, R12It is independently selected from hydrogen, the alkyl of C1~C12, C3~
The naphthenic base of C12, the alkenyl of C2~C12, any one of alkynyl or the aryl of C6~C20 of C2~C12；
Wherein, work as R5, R6, R7, R8, R9, R10, R11, R12In at least one R base when not being hydrogen, this is not arbitrary on the R base of hydrogen
Hydrogen atom is optional substituted or non-substituted.
5. electrolysis additive according to claim 4, which is characterized in that formula (II) compound structure such as following formula (III)
It is shown:
In formula (III), R6, R7, R10, R11It is independently selected from the alkyl of C1~C12, the naphthenic base of C3~C12, C2~C12
Alkenyl, any one of alkynyl or the aryl of C6~C20 of C2~C12；
Wherein, R6, R7, R10, R11Upper arbitrary hydrogen atom is optional substituted or non-substituted.
6. a kind of electrolyte, which is characterized in that the electrolyte includes electrolyte addition of any of claims 1-5
Agent and basic electrolyte.
7. electrolyte according to claim 6, which is characterized in that the quality of electrolysis additive is basic electrolyte quality
0.01~5%；
It wherein, include carbonate solvent and lithium salts in the basic electrolyte；
Preferably, the quality of electrolysis additive is the 0.05~3% of basic electrolyte quality.
8. a kind of method for preparing the electrolyte of claim 6 or 7, which is characterized in that the preparation method includes following step
It is rapid:
Electrolysis additive of any of claims 1-5 is added into basic electrolyte to get electrolyte is arrived.
9. including the lithium ion battery of the electrolyte of claim 6 or 7.
10. the equipment driven by lithium ion battery as claimed in claim 9.
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